Stabilized body care products, household products, textiles and fabrics

ABSTRACT

Disclosed are stabilized body care products, household products, textiles and fabrics which comprise certain sterically hindered amine salt compounds. Dyed products and articles are effectively stabilized against color degradation. The products are for example skin-care products, hair-care products, dentifrices, cosmetics, laundry detergents and fabric softeners, non-detergent based fabric care products, household cleaners and textile-care products.

This application is a divisional of application Ser. No. 11/201,377,filed Aug. 10, 2005, now U.S. Pat. No. 7,410,936, which claims benefitunder 35 USC 119(e) of U.S. provisional application No. 60/603,590,filed Aug. 23, 2004, the disclosure of which is hereby incorporated byreference.

The present invention relates to the use of certain sterically hinderedamine salt compounds for the protection of body care products, householdproducts, textiles and fabrics against the deleterious effects of light,heat and oxygen.

The stabilized compositions for example comprise dyes that arestabilized against color change.

BACKGROUND

WO 00/25730 and WO 00/25731 are aimed at the stabilization of body careand household products.

U.S. Pat. app. No. 60/377,381, filed May 2, 2002, discloses the use ofselected hindered nitroxyl, hydroxylamine and hydroxylamine saltcompounds in formulations of body care products, household products,textiles and fabrics, and is incorporated herein by reference.

WO 01/07550 teaches the treatment of fabric with hindered aminestabilizers.

U.S. Pat. No. 6,254,724 teaches the stabilization of pulp and paper withhindered-amine based compounds.

It is now found that certain sterically hindered amine salt compoundsprovide outstanding protection against light-induced fading of homepersonal care products.

DETAILED DISCLOSURE

The present invention pertains to a stabilized composition comprising

(a) a body care product, household product, textile or fabric and

(b) an effective stabilizing amount of one or more compounds of formula(I)

whereinG₁ and G₂ are independently alkyl of 1 to 4 carbon atoms or are togetherpentamethylene; Z₁ and Z₂ are each methyl, or Z₁ and Z₂ together form anunsubstituted linking moiety or a linking moiety substituted by one ormore groups selected from an ester, ether, hydroxy, oxo, cyanohydrin,amide, amino, carboxy or an urethane group;E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atomsor aralkoxy of 7 to 15 carbon atoms, or E is —O-T-(OH)_(b),T is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbonatoms, a straight or branched chain alkylene of 1 to 4 carbon atomssubstituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms;b is 1, 2 or 3 with the proviso that b cannot exceed the number ofcarbon atoms in T, and when b is 2 or 3, each hydroxyl group is attachedto a different carbon atoms of T; andHY is an inorganic or organic acid; wherein the total charge of cationsis equal to the total charge of anions.

For example, Y is phosphate, phosphonate, carbonate, bicarbonate,nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate,borate, formate, acetate, benzoate, citrate, oxalate, tartrate,acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate,gluconate, malate, mandelate, tiglate, ascorbate, polymethacrylate, acarboxylate of nitrilotriacetic acid, a carboxlylate ofhydroxyethylethylenediaminetriacetic acid, a carboxylate ofethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, a carboxylate ofdiethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, alkylsulfonate, arylsulfonate, oralkyl-substituted arylsulfonate.

Y is a carboxylate, especially a carboxylate of a mono-, di-, tri- ortetracarboxylic acid, mainly of 1-18 carbon atoms, such as a formate,acetate, benzoate, citrate, or oxalate.

For example, Y is chloride, bisulfate, sulfate, phosphate, nitrate,ascorbate, formate, acetate, benzoate, oxalate, citrate, a carboxylateof ethylenediaminetetraacetic acid or of diethylenetriaminepentaaceticacid or polyacrylate.

For instance, Y is chloride, bisulfate, ascorbate, or citrate.

The total charge for the salt is neutral. For example, the total numberof cations is equal to the total number of anions.

The certain hindered amine compounds described herein are acid salts ofthe corresponding hindered amine compounds.

For example, Z1 and Z2 together are a hydrocarbon linking moietycontaining 1-200 carbon and heteroatoms; for instance, 1-60 carbon atomsand 0-60 heteroatoms; especially, 0-30 heteroatoms selected from oxygenatoms and nitrogen atoms.

For instance, Z1 and Z2 as a linking moiety are a chain of 2 or 3 carbonatoms or 1 or 2 carbon atoms and a nitrogen or oxygen atom formingtogether with the remaining structure in formula (I) a saturatedunsubstituted 5- or 6-membered heterocyclic ring or a 5- or 6-memberedheterocyclic ring substituted by one or more groups selected from anester, ether, hydroxy, oxo, cyanohydrin, amide, amino, carboxy or anurethane group. The substituents in Z1 and Z2 themselves may containhindered amine moieties. For example, the compounds of the formula (I)contain 1-4 hindered amine or hindered ammonium groups. For instance,the compounds of formula (I) contain 1 or 2 hindered amine or hinderedammonium moieties.

Any group denoted as aryl mainly means C₆-C₁₂aryl; for example, aryl isphenyl or naphthyl; for instance, aryl is phenyl.

Group denoted as alkyl are, within the definitions given, mainlyC₁-C₁₈alkyl, for example methyl, ethyl, propyl such as n- or isopropyl,butyl such as n-, iso-, sec- and tert-butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, or octadecyl.

Groups denoted as alkylene are, within the definitions given, forexample methylene, 1,2-ethylene, 1,1-ethylene, 1,3-propylene,1,2-propylene, 1,1-propylene, 2,2-propylene, 1,4-butylene, 1,3-butylene,1,2-butylene, 1,1-butylene, 2,2-butylene, 2,3-butylene, or —C₅H₁₀—,—C₆H₁₂—, C₇H₁₄, —C₈H₁₆—, —C₉H₁₈—, —C₁₀H₂O—, —C₁₁H₂₂—, —C₁₂H₂₄—,—C₁₃H₂₆—, —C₁₄H₂₈—, —C₁₅H₃₀—, —C₁₆H₃₂—, —C₁₇H₃₄—, or —C₁₈H₃₆—.

Groups denoted as cycloalkyl or cycloalkoxy are mainly C₅-C₁₂cycloalkylor C₅-C₁₂cycloalkoxy, the cycloalkyl part being, for example,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cycloundecyl, or cyclododecyl. Cycloalkenyl is mainlyC₅-C₁₂cycloalkenyl including cyclopentenyl, cyclohexenyl, cycloheptenyl,cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, orcyclododecenyl.

Aralkyl or aralkoxy is, for example, phenylalkyl or phenylalkoxy, whichis alkyl or alkoxy substituted by phenyl. Examples for phenylalkyl orphenylalkoxy are, within the definitions given, benzyl, benzyloxy,alpha-methylbenzyl, alpha-methylbenzyloxy, cumyl, or cumyloxy.

Alkenyl residues are mainly alkenyl of 2 to 18 carbon atoms; forexample, allyl.

Alkynyl residues are mainly alkynyl of 2 to 12 carbon atoms; forexample, propargyl.

A group denoted as acyl is mainly R(C═O)—, where R is an aliphatic oraromatic moiety.

An aliphatic or aromatic moiety, such as mentioned above or otherdefinitions, mainly is an aliphatic or aromatic C₁-C₃₀hydrocarbon;examples are aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl,bicycloalkyl, bicycloalkenyl, and combinations of these groups.

Examples for acyl groups are alkanoyl of 2 to 12 carbon atoms, alkenoylof 3 to 12 carbon atoms, or benzoyl.

Alkanoyl embraces, for example, formyl, acetyl, propionyl, butyryl,pentanoyl, oroctanoyl; for example, C₂-C₈alkanoyl; for instance, acetyl.

Alkenoyl residues are, for example, acryloyl, or methacryloyl.

The alkyl groups in the different substituents may be linear orbranched.

Examples for alkenyl groups with 2 to 4 carbon atoms are ethenyl,propenyl, or butenyl. Examples for alkyl groups with 1 to 4 carbon atomsinterrupted by one or two oxygen atoms are —CH₂—O—CH₃, —CH₂—CH₂—O—CH₃,—CH₂—CH₂—O—CH₂—CH₃, —CH₂—O—CH₂—CH₂—O—CH₃ or —CH₂—O—CH₂—O—CH₃.

Examples for hydroxy substituted alkyl groups with 2 to 6 carbon atomsare hydroxy ethyl, di-hydroxy ethyl, hydroxy propyl, di-hydroxy propyl,hydroxy butyl, hydroxy pentyl, or hydroxy hexyl.

Examples of especially suited compounds of component (b) formula (I) areselected from the group consisting of formulae A* to EE* and (III) to(IIIc):

whereinE is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atomsor aralkoxy of 7 to 15 carbon atoms, or E is —O-T-(OH)_(b),T is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbonatoms, a straight or branched chain alkylene of 1 to 4 carbon atomssubstituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms;b is 1, 2 or 3 with the proviso that b cannot exceed the number ofcarbon atoms in T, and when b is 2 or 3, each hydroxyl group is attachedto a different carbon atoms of T;R is hydrogen or methyl; andin formula (A*) n is 1 or 2,when n is 1,R₁ is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl of 2-18 carbonatoms, propargyl, glycidyl, alkyl of 2 to 50 carbon atoms interrupted byone to twenty oxygen atoms, said alkyl substituted by one to tenhydroxyl groups or both interrupted by said oxygen atoms and substitutedby said hydroxyl groups, orR₁ is alkyl of 1 to 4 carbon atoms substituted by a carboxy group or by—COOZ where Z is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl, orwhere Z is said alkyl substituted by —(COO⁻)_(n)M^(n+) where n is 1-3and M is a metal ion from the 1st, 2nd or 3rd group of the periodictable or is Zn, Cu, Ni or Co, or M is a group N^(n+) (R₂)₄ where R₂ isalkyl of 1 to 8 carbon atoms or benzyl,when n is 2,R₁ is alkylene of 1 to 12 carbon atoms, alkenylene of 4 to 12 carbonatoms, xylylene or alkylene of 1 to 50 carbon atoms interrupted by oneto twenty oxygen atoms, substituted by one to ten hydroxyl groups orboth interrupted by said oxygen atoms and substituted by said hydroxylgroups;in formula (B*), m is 1 to 4, andwhen m is 1,R₂ is alkyl of 1 to 18 carbon atoms, alkyl of 3 to 18 carbon atomsinterrupted by —COO—, alkyl of 3 to 18 carbon atoms substituted by COOHor COO—, or R₂ is —CH₂(OCH₂CH₂)_(n)OCH₃where n is 1 to 12, orR₂ is cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 12 carbon atoms,or said aryl substituted by one to four alkyl groups of 1 to 4 carbonatoms, orR₂ is —NHR₃ where R₃ is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5to 12 carbon atoms, aryl of 6 to 12 carbon atoms, or said arylsubstituted by one to four alkyl of 1 to 4 carbon atoms, orR₂ is —N(R₃)₂ where R₃ is as defined above,when m is 2,R₂ is alkylene of 1 to 12 carbon atoms, alkenylene of 4 to 12 carbonatoms, xylylene, alkylene of 2 to 12 carbon atoms interrupted by —COO—,alkylene of 3 to 18 carbon atoms substituted by COOH or COO—, or R₂ is—CH₂(OCH₂CH₂)_(n)OCH₂— where n is 1 to 12, orR₂ is cycloalkylene of 5 to 12 carbon atoms, aralkylene of 7 to 15carbon atoms or arylene of 6 to 12 carbon atoms, orR₂ is —NHR₄NH— where R₄ is alkylene of 2 to 18 carbon atoms,cycloalkylene of 5 to 12 carbon atoms, aralkylene of 8 to 15 carbonatoms or arylene of 6 to 12 carbon atoms, orR₂ is —N(R₃)R₄N(R₃)— where R₃ and R₄ are as defined above, orR₂ is —CO—, —NH—CO—NH—, or —N(R₃)—CO—N(R₃)—,when m is 3,R₂ is alkanetriyl of 3 to 8 carbon atoms or benzenetriyl, orwhen m is 4,R₂ is alkanetetrayl of 5 to 8 carbon atoms or benzenetetrayl,in formula (C*),R₁₀ is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, aralkyl of 7 to 15 carbon atoms, alkanoyl of 2 to 18carbon atoms, alkenoyl of 3 to 5 carbon atoms or benzoyl,x is 1 or 2, andwhen x is 1,R₁₁ is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl of 2 to 18carbon atoms, propargyl, glycidyl, alkyl of 2 to 50 carbon atomsinterrupted by one to twenty oxygen atoms, said alkyl substituted by oneto ten hydroxyl groups or both interrupted by said oxygen atoms andsubstituted by said hydroxyl groups, orR₁₁ is alkyl of 1 to 4 carbon atoms substituted by a carboxy group or by—COOZ where Z is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl, orwhere Z is said alkyl substituted by —(COO⁻)_(n)M^(n+) where n is 1-3and M is a metal ion from the 1st, 2nd or 3rd group of the periodictable or is Zn, Cu, Ni or Co, or M is a group N^(n+) (R₂)₄ where R₂ ishydrogen, alkyl of 1 to 8 carbon atoms or benzyl, orwhen x is 2,R₁₁ is alkylene of 1 to 12 carbon atoms, alkenylene of 4 to 12 carbonatoms, xylylene or alkylene of 1 to 50 carbon atoms interrupted by oneto twenty oxygen atoms, substituted by one to ten hydroxyl groups orboth interrupted by said oxygen atoms and substituted by said hydroxylgroups,in formula (D*), y is 1 to 4,R₁₀ is as defined above,and R₁₂ is defined as R₂ above,in formula (E*), k is 1 or 2,when k is 1,R₂₀ and R₂₁ are independently alkyl of 1 to 12 carbon atoms, alkenyl of2 to 12 carbon atoms or aralkyl of 7 to 15 carbon atoms, or R₂₀ is alsohydrogen, orR₂₀ and R₂₁ together are alkylene of 2 to 8 carbon atoms or saidalkylene substituted by hydroxyl, or are acyloxy-alkylene of 4 to 22carbon atoms, orwhen k is 2,R₂₀ and R₂₁ are together (—CH₂)₂C(CH₂—)₂,in formula (F*),R₃₀ is hydrogen, alkyl of 1 to 18 carbon atoms, benzyl, glycidyl, oralkoxyalkyl of 2 to 6 carbon atoms,g is 1 or 2,when g is 1, R₃₁ is defined as R₁ above when n is 1,when g is 2, R₃₁ is defined as R₁ above when n is 2,in formula (G*),Q₁ is —NR₄₁— or —O—,E₁ is alkylene of 1 to 3 carbon atoms, or E₁ is —CH₂—CH(R₄₂)—O— whereR₄₂ is hydrogen, methyl or phenyl, or E₁ is —(CH₂)₃—NH— or E₁ is adirect bond,R₄₀ is hydrogen or alkyl of 1 to 18 carbon atoms,R₄₁ is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbonatoms, or R₄₁ is —CH₂—CH(R₄₂)—OH where R₄₂ is as defined above,in formula (H*), p is 1 or 2,T₄ is as defined for R₁₁ when x is 1 or 2,M and Y are independently methylene or carbonyl, preferably M ismethylene and Y is carbonyl,in formula (I*),this formula denotes a recurring structural unit of a polymer where T₁is ethylene or 1,2-propylene or is the repeating structural unit derivedfrom an alpha-olefin copolymer with an alkyl acrylate or methacrylate,and whereq is 2 to 100,Q₁ is —N(R₄₁)— or —O— where R₄₁ is as defined above,in formula (J*),r is 1 or 2,T₇ is as defined for R₁ when n is 1 or 2 in formula (A*), preferably T₇is octamethylene when r is 2,in formula (L*), u is 1 or 2,T₁₃ is as defined for R₁ when n is 1 or 2 in formula (A*), with theproviso that T₁₃ is not hydrogen when u is 1,in formula (M*),E₁ and E₂, being different, each are —CO— or —N(E₅)- where E₅ ishydrogen, alkyl of 1 to 12 carbon atoms or alkoxycarbonylalkyl of 4 to22 carbon atoms, preferably E₁ is —CO— and E₂ is —N(E₅)-,E₃ is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, saidphenyl or said naphthyl substituted by chlorine or by alkyl of 1 to 4carbon atoms, or phenylalkyl of 7 to 12 carbon atoms, or saidphenylalkyl substituted by alkyl of 1 to 4 carbon atoms,E₄ is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl orphenylalkyl of 7 to 12 carbon atoms, orE₃ and E₄ together are polymethylene of 4 to 17 carbon atoms, or saidpolymethylene substituted by one to four alkyl of 1 to 4 carbon atoms,preferably methyl,in formula (O*),R₁₀ is as defined for R₁₀ in formula (C*),in formula (P*),E₆ is an aliphatic or aromatic tetravalent radical, preferablyneopentanetetrayl or benzenetetrayl,in formula (T*),R₅₁ is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, or aryl of 6 to 10 carbon atoms,R₅₂ is hydrogen or alkyl of 1 to 18 carbon atoms, orR₅₁ and R₅₂ together of alkylene of 4 to 8 carbon atoms,f is 1 or 2,when f is 1,R₅₀ is as defined for R₁₁ in formula (C*) when x is 1, or R₅₀ is—(CH₂)_(z)COOR₅₄ where z is 1 to 4 and R₅₄ is hydrogen or alkyl of 1 to18 carbon atoms, or R₅₄ is a metal ion from the 1st, 2nd or 3rd group ofthe periodic table or a group —N(R₅₅)₄ where R₅₅ is hydrogen, alkyl of 1to 12 carbon atoms or benzyl,when f is 2,R₅₀ is as defined for R₁₁ in formula (C*) when x is 2,in formula (U*),R₅₃, R₅₄, R₅₅ and R₅₆ are independently alkyl of 1 to 4 carbon atoms orare together pentamethylene,in formula (V*),R₅₇, R₅₈, R₅₉ and R₆₀ are independently alkyl of 1 to 4 carbon atoms orare together pentamethylene,in formula (W*),R₆₁, R₆₂, R₆₃ and R₆₄ are independently alkyl of 1 to 4 carbon atoms orare together pentamethylene,R₆₅ is alkyl of 1 to 5 carbon atoms,M is hydrogen or oxygen,wherein in formulas (Y*) to (BB*),n is 2 to 3,G₁ is hydrogen, methyl, ethyl, butyl or benzyl,m is 1 to 4,x is 1 to 4,when x is 1, R₁ and R₂ are independently alkyl of 1 to 18 carbon atoms,said alkyl interrupted by one to five oxygen atoms, said alkylsubstituted by 1 to 5 hydroxyl groups or said alkyl both interrupted bysaid oxygen atoms and substituted by said hydroxyl groups; cycloalkyl of5 to 12 carbon atoms, aralkyl of 7 to 15 carbon atoms, aryl of 6 to 10carbon atoms or said aryl substituted by one to three alkyl of 1 to 8carbon atoms, or R₁ is also hydrogen, or R₁ and R₂ are togethertetramethylene, pentamethylene, hexamethylene or 3-oxapentamethylene,when x is 2,R₁ is hydrogen, alkyl of 1 to 8 carbon atoms, said alkyl interrupted byone or two oxygen atoms, said alkyl substituted by a hydroxyl group, orsaid alkyl both interrupted by one or two oxygen atoms and substitutedby a hydroxyl group,R₂ is alkylene of 2 to 18 carbon atoms, said alkylene interrupted by oneto five oxygen atoms, said alkylene substituted by 1 to 5 hydroxylgroups or said alkylene both interrupted by said oxygen atoms andsubstituted by said hydroxyl groups; o-, m- or p-phenylene or saidphenylene substituted by one or two alkyl of 1 to 4 carbon atoms, orR₂ is —(CH₂)_(k)O[(CH₂)_(k)O]_(h)(CH₂)_(k)— where k is 2 to 4 and h is 1to 40, orR₁ and R₂ together with the two N atoms to which they are attached arepiperazin-1,4-diyl, when x is 3,R₁ is hydrogen,R₂ is alkylene of 4 to 8 carbon atoms interrupted by one nitrogen atom,when x is 4,R₁ is hydrogen,R₂ is alkylene of 6 to 12 carbon atoms interrupted by two nitrogenatoms,R₃ is hydrogen, alkyl of 1 to 8 carbon atoms, said alkyl interrupted byone or two oxygen atoms, said alkyl substituted by a hydroxyl group, orboth interrupted by one or two oxygen atoms and substituted by ahydroxyl group,p is 2 or 3,in formula (DD*),m is 2 or 3,when m is 2,G is —(CH₂CHR—O)_(r)CH₂CHR—, where r is 0 to 3, and R is hydrogen ormethyl, andwhen m is 3, G is glyceryl,in formula (EE*),G₂ is —CN, —CONH₂ or —COOG₃ where G₃ is hydrogen, alkyl of 1 to 18carbon atoms or phenyl,in formulae (III) to (IIIc),A11 is OR₁₀₁ or NR₁₁₁R₁₁₂,R₁₀₁ is alkenyl of 2 to 4 carbon atoms, propargyl, glycidyl, alkyl of 2to 6 carbon atoms interrupted by one or two oxygen atoms, substituted byone to three hydroxyl groups or both interrupted by said oxygen atomsand substituted by said hydroxyl groups, or R₁₀₁ is alkyl of 1 to 4carbon atoms substituted by carboxy or by the alkali metal, ammonium orC₁-C₄alkylammonium salts thereof; or R₁₀₁ is alkyl substituted by COOE₁₀where E₁₀ is methyl or ethyl,R₁₀₂ is alkyl of 3 to 5 carbon atoms interrupted by —COO— or by —CO—, orR₁₀₂ is —CH₂(OCH₂CH₂)_(c)COCH₃ where c is 1 to 4; orR₁₀₂ is —NHR₁₀₃ where R₁₀₃ is alkyl of 1 to 4 carbon atoms,a is 2 to 4,when a is 2,T₁₁ is —(CH₂CHR₁₀₀—O)_(d)CH₂CHR₁₀₀—, where d is 0 or 1, and R₁₀₀ ishydrogen or methyl,when a is 3, T₁₁ is glyceryl,when a is 4, T₁₁ is neopentanetetrayl,b is 2 or 3,when b is 2,G₁₁ is —(CH₂CHR₁₀₀—O)_(d)CH₂CHR₁₀₀—, where d is 0 or 1, and R₁₀₀ ishydrogen or methyl, and when b is 3, G₁₁ is glyceryl;R₁₁₁ is hydrogen, unsubstituted alkyl of 1 to 4 carbon atoms, alkyl of 1to 4 carbon atoms substituted by one or two hydroxyl, alkyl of 1 to 4carbon atoms interrupted by one or two oxygen atoms, or both substitutedby one hydroxyl and interrupted by one or two oxygen atoms,R₁₁₂ is —CO—R₁₁₃ where R₁₁₃ has the same meaning as R₁₁₁, or R₁₁₃ isNHR₁₁₄, wherein R₁₁₄ is unsubstituted alkyl of 1 to 4 carbon atoms,alkyl of 1 to 4 carbon atoms substituted by one or two hydroxyl, alkylof 1 to 4 carbon atoms substituted by alkoxy of 1 to 2 carbon atoms, orboth substituted by one hydroxyl and by alkoxy of 1 to 2 carbon atoms,orR₁₁₁ and R₁₁₂ together are —CO—CH₂CH₂—CO—, or (CH₂)₆CO—;HY is an inorganic or organic acid; wherein the total charge of cationsis equal to the total charge of anions; andY is phosphate, phosphonate, carbonate, bicarbonate, nitrate, chloride,bromide, bisulfite, sulfite, bisulfate, sulfate, borate, formate,acetate, benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate,fumarate, maleate, itaconate, glycolate, gluconate, malate, mandelate,tiglate, ascorbate, polymethacrylate, a carboxylate of nitrilotriaceticacid, a carboxlylate of hydroxyethylethylenediaminetriacetic acid, acarboxylate of ethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, a carboxylate ofdiethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, alkylsulfonate, arylsulfonate, oralkyl-substituted arylsulfonate.

Another embodiment of the instant invention is the compounds ofcomponent (b) formula (I) selected from the group consisting of (A*),(B*), (C*), (D*), (Q*), (R*), (Y*), and (Z*),

wherein

E is alkoxy of 1 to 10 carbon atoms, cycloalkoxy of 5 to 8 carbon atomsor aralkoxy of 7 to 12 carbon atoms, or E is —O-T-(OH)_(b),

T is a straight or branched chain alkylene of 1 to 10 carbon atoms,cycloalkylene of 5 to 10 carbon atoms, cycloalkenylene of 5 to 10 carbonatoms, a straight or branched chain alkylene of 1 to 4 carbon atomssubstituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms;b is 1, 2 or 3 with the proviso that b cannot exceed the number ofcarbon atoms in T, and when b is 2 or 3, each hydroxyl group is attachedto a different carbon atoms of T;R is hydrogen;in formula (A*), n is 1 or 2,when n is 1,R₁ is hydrogen, alkyl of 1 to 6 carbon atoms, alkenyl of 2-6 carbonatoms, propargyl, glycidyl, alkyl of 2 to 20 carbon atoms interrupted byone to ten oxygen atoms, said alkyl substituted by one to five hydroxylgroups or both interrupted by said oxygen atoms and substituted by saidhydroxyl groups, orR₁ is alkyl of 1 to 4 carbon atoms substituted by a carboxy group or by—COOZ where Z is hydrogen or alkyl of 1 to 4 carbon atoms,when n is 2,R₁ is alkylene of 1 to 8 carbon atoms, alkenylene of 4 to 8 carbonatoms, alkylene of 1 to 20 carbon atoms interrupted by one to ten oxygenatoms, substituted by one to five hydroxyl groups or both interrupted bysaid oxygen atoms and substituted by said hydroxyl groups,in formula (B*), m is 1 or 2,when m is 1,R₂ is alkyl of 1 to 4 carbon atoms or R₂ is CH₂(OCH₂CH₂)_(n)OCH₃ where nis 1 to 12, orR₂ is phenyl, or said phenyl substituted by one to three methyl groups,orR₂ is —NHR₃ where R₃ is alkyl of 1 to 4 carbon atoms or phenyl, or saidphenyl substituted by one or two methyl groups,when m is 2,R₂ is alkylene of 1 to 8 carbon atoms, alkenylene of 4 to 8 carbonatoms, or R₂ is —CH₂(OCH₂CH₂)_(n)OCH₂— where n is 1 to 12, orR₂ is —NHR₄NH— where R₄ is of 2 to 6 carbon atoms, aralkylene of 8 to 15carbon atoms or arylene of 6 to 12 carbon atoms, orR₂ is —CO— or —NHCONH—,in formula (C*),R₁₀ is hydrogen or, alkanoyl of 1 to 3 carbon atoms,x is 1 or 2,when x is 1,R₁₁ is hydrogen, alkyl of 1 to 6 carbon atoms or glycidyl, orR₁₁ is alkyl of 1 to 4 carbon atoms substituted by a carboxy group or byCOOZ where Z is hydrogen or alkyl of 1 to 4 carbon atoms,when x is 2,R₁₁ is alkylene of 1 to 6 carbon atoms,in formula (D*),R₁₀ is hydrogen,y is 1 or 2,R₁₂ is defined as R₂ above,in formula (Y*) and (Z*),x is 1 or 2,when x is 1,R₁ and R₂ are independently alkyl of 1 to 4 carbon atoms or R₁ and R₂are together tetramethylene, or pentamethylene,R₂ is hydrogen or alkyl of 1 to 4 carbon atoms, said alkyl groupsubstituted by a hydroxyl group,when x is 2,R₁ is hydrogen, alkyl of 1 to 4 carbon atoms, said alkyl substituted bya hydroxyl group,R₂ is alkylene of 2 to 6 carbon atoms,R₃ is as defined above,HY is an inorganic or organic acid; wherein the total charge of cationsis equal to the total charge of anions; andY is phosphate, phosphonate, carbonate, bicarbonate, chloride, bromide,bisulfate, sulfate, borate, formate, acetate, benzoate, citrate,oxalate, tartrate, acrylate, fumarate, maleate, itaconate, glycolate,gluconate, malate, mandelate, tiglate, ascorbate, a carboxylate ofnitrilotriacetic acid, a carboxylate ofhydroxyethylethylenediaminetriacetic acid, a carboxylate ofethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, a carboxylate ofdiethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, alkylsulfonate, arylsulfonate, oralkyl-substituted arylsulfonate.

Still another embodiment of the instant invention is the compounds ofcomponent (b) formula (I) selected from the group consisting of (A*),(B*), (C*), (D*), (Q*), and (R*),

wherein

E is alkoxy of 1 to 10 carbon atoms, cycloalkoxy of 5 to 8 carbon atomsor aralkoxy of 7 to 12 carbon atoms, or E is —O-T-(OH)_(b),

T is a straight or branched chain alkylene of 1 to 10 carbon atoms,cycloalkylene of 5 to 10 carbon atoms, cycloalkenylene of 5 to 10 carbonatoms, a straight or branched chain alkylene of 1 to 4 carbon atomssubstituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms;b is 1, 2 or 3 with the proviso that b cannot exceed the number ofcarbon atoms in T, and when b is 2 or 3, each hydroxyl group is attachedto a different carbon atoms of T;R is hydrogen,in formula (A*),n is 1,R₁ is hydrogen, alkyl of 1 to 4 carbon atoms, glycidyl, alkyl of 2 to 4carbon atoms interrupted by one or two oxygen atoms, said alkylsubstituted by one or two hydroxyl groups or both interrupted by saidoxygen atoms and substituted by said hydroxyl groups, orR₁ is alkyl of 1 to 4 carbon atoms substituted by —COOZ where Z ishydrogen or alkyl of 1 to 4 carbon atoms,in formula (B*),m is 1 or 2,R₂ is alkyl of 1 to 4 carbon atoms or R₂ is CH₂(OCH₂CH₂)_(n)OCH₃ where nis 1 to 4,when m is 2,R₂ is alkylene of 1 to 8 carbon atoms,in formula (C*),R₁₀ is hydrogen or alkanoyl of 1 or 2 carbon atoms,x is 1 or 2,when x is 1,R₁₁ is hydrogen, alkyl of 1 to 4 carbon atoms or glycidyl,R₁₁ is alkyl of 1 to 4 carbon atoms substituted by COOZ where Z ishydrogen or alkyl of 1 to 4 carbon atoms,when x is 2,R₁₁ is alkylene of 1 to 6 carbon atoms,in formula (D*),R₁₀ is hydrogen,y is 1 or 2,R₁₂ is defined as R₂ above;HY is an inorganic or organic acid; wherein the total charge of cationsis equal to the total charge of anions; andY is phosphate, phosphonate, carbonate, bicarbonate, chloride, bromide,bisulfate, sulfate, borate, formate, acetate, benzoate, citrate,oxalate, tartrate, ascorbate, acrylate, fumarate, maleate, itaconate,glycolate, gluconate, malate, mandelate, tiglate, a carboxylate ofnitrilotriacetic acid, a carboxylate ofhydroxyethylethylenediaminetriacetic acid, a carboxylate ofethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, a carboxylate ofdiethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, alkylsulfonate, arylsulfonate, oralkyl-substituted arylsulfonate.

Yet another embodiment of the instant invention is a compound ofcomponent (b) formula (I) selected from the group consisting of

-   (a) bis(1-octyloxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate    hydrochloride;-   (b) 1-methoxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium citrate;-   (c) 1-methoxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium phosphate;-   (d) 1-butoxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium bisulfate;-   (e) 1-methoxy-2,2,6,6-tetramethyl-4-oxo-piperidinium methyl    sulfonate;-   (f) 1-methoxy-2,2,6,6-tetramethyl-4-oxo-piperidinium acetate;-   (g) 1-phenoxy-2,2,6,6-tetramethyl-4-methoxy-piperidinium tartrate;-   (h) 1-benzoxy-2,2,6,6-tetramethyl-4-methoxy-piperidinium acetate;-   (i) 1-ethoxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium maleate;-   (j) 1-methoxy-2,2,6,6-tetramethyl-4-propoxy-piperidinium mandelate;-   (k) 1-methoxy-2,2,6,6-tetramethyl-4-propoxy-piperidinium oxalate;-   (l)    1-methoxy-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidinium    bicarbonate;-   (m)    1-methoxy-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidinium    glycolate;-   (n) 1-methoxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium gluconate;-   (o) 1-methoxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium ascorbate;-   (p) 1-methoxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium benzene    sulfonate;-   (q)    1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium    ascorbate;-   (r)    1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium    citrate;-   (s)    bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate;-   (t)    tris(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate;-   (u)    tetra(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)ethylenediaminetetraacetate;-   (v)    tetra(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-acetamidopiperidinium)ethylenediaminetetraacetate;-   (w)    tetra(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-oxopiperidinium)ethylenediaminetetraacetate;-   (x)    penta(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)diethylenetriaminepentaacetate;-   (y)    penta(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-acetamidopiperidinium)diethylenetriaminepentaacetate;-   (z)    penta(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-oxopiperidinium)diethylenetriaminepentaacetate;-   (aa)    tri(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)nitrilotriacetate;-   (bb)    tri(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-acetamidopiperidinium)nitrilotriacetate;-   (cc)    tri(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-oxopiperidinium)nitrilotriacetate;-   (dd)    penta(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)diethylenetriaminepentamethylenephosphonate;-   (ee)    penta(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-acetamidopiperidinium)diethylenetriaminepentamethylenephosphonate;    and,-   (ff)    penta(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-oxopiperidinium)diethylenetriaminepentamethylenephosphonate.

Another embodiment of the instant invention is a compound of component(b) formula (I) selected from the group consisting of

-   (a) bis(1-octyloxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate    hydrochloride;-   (b) 1-methoxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium citrate;-   (c) 1-butoxy-2,2,6,6-tetramethyl-4-acetamidopiperidinium bisulfate;-   (d) 1-methoxy-2,2,6,6-tetramethyl-4-oxo-piperidinium methyl    sulfonate;-   (e) 1-methoxy-2,2,6,6-tetramethyl-4-oxo-piperidinium acetate;-   (f) 1-ethoxy-2,2,6,6-tetramethyl-4-acetoxypiperidinium maleate;-   (g) 1-methoxy-2,2,6,6-tetramethyl-4-propoxy-piperidinium oxalate;-   (h)    1-methoxy-2,2,6,6-tetramethyl-4-(2-hydroxy-4-oxapentoxy)piperidinium    glycolate;-   (i) 1-methoxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium ascorbate;-   (j) 1-methoxy-2,2,6,6-tetramethyl-4-hydroxypiperidinium benzene    sulfonate;-   (k)    1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium    ascorbate;-   (l)    1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium    citrate;-   (m)    bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate;-   (n)    tris(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)citrate;-   (o)    tetra(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)ethylenediaminetetraacetate;-   (p)    tetra(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-acetamidopiperidinium)ethylenediaminetetraacetate;-   (q)    penta(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)diethylenetriaminepentaacetate;-   (r)    tri(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)nitrilotriacetate;-   (s)    penta(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidinium)diethylenetriaminepentamethylenephosphonate;    and,-   (t)    penta(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-acetamidopiperidinium)diethylenetriaminepentamethylenephosphonate.

The compounds of component (b) formula (I) can be prepared according tomethods known in the art or in analogy to those methods. For example,these compounds may be prepared according to U.S. Pat. No. 6,392,041;U.S. Pat. No. 6,586,507; U.S. Pat. No. 6,166,212; U.S. Pat. No.5,374,729; U.S. Pat. No. 5,015,683; U.S. Pat. No. 5,021,483; U.S. Pat.No. 4,921,962; U.S. Pat. No. 5,112,890; and, U.S. Pat. No. 5,204,473,incorporated herein by reference.

The present compositions may comprise further traditional additives, forexample ultraviolet (UV) light absorbers and antioxidants.

The present invention pertains to a stabilized composition comprising

-   -   (a) a body care product, household product, textile or fabric,    -   (b) an effective stabilizing amount of one or more compounds of        formula (I), and    -   (c) one or more compounds selected from the group consisting of        the ultraviolet light absorbers, antioxidants, tocopherol,        tocopherol acetate, hindered amine light stabilizers, complex        formers, optical brighteners, surfactants, and        polyorganosiloxanes.

The additional additives of present component (c) are for example thosedisclosed in co-pending U.S. application Ser. No. 09/830,788, filed May1, 2001 and 09/830,787, filed May 1, 2001, published as WO 00/25730 andWO 00/25731. The disclosures of these co-pending applications are herebyincorporated by reference.

The UV absorbers are for example selected from group consisting of the2H-benzotriazoles, the s-triazines, the benzophenones, thealpha-cyanoacrylates, the oxanilides, the benzoxazinones, the benzoatesand the alpha-alkyl cinnamates.

The UV absorbers are for example

-   2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine;-   2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;-   2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine;-   2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine;-   2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;-   2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;-   2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;-   2-[2-hydroxy-4-(2-hydroxy-3-tridecyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;-   5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;-   2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;-   5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;-   bis-(3-(2H-benzotriazol-2-yl)-2-hydroxy-5-tert-octyl)methane;-   2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;-   2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;-   2-(2-hydroxy-3,5-di-alpha?cumylphenyl)-2H-benzotriazole;-   2-(2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl)-2H-benzotriazole;-   2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;-   3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonic    acid monosodium salt;-   3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamic acid    and sodium salt;-   12-hydroxy-3,6,9-trioxadodecyl    3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamate;-   octyl    3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamate;-   4,6-bis(2,4-dimethylphenyl)-2-(4-(3-dodecyloxy*-2-hydroxypropoxy)-2-hydroxyphenyl)-s-triazine    (*is mixture of C₁₂₋₁₄oxy isomers);-   4,6-bis(2,4-dimethylphenyl)-2-(4-octyloxy-2-hydroxyphenyl)-s-triazine;-   2,4-dihydroxybenzophenone;-   2,2′-dihydroxy-4,4′-dimethoxy-5,5′-disulfobenzophenone, disodium    salt;-   2-hydroxy-4-octyloxybenzophenone;-   2-hydroxy-4-dodecyloxybenzophenone;-   2,4-dihydroxybenzophenone;-   2,2′,4,4′-tetrahydroxybenzophenone;-   4-aminobenzoic acid;-   2,3-dihydroxypropyl-4-aminobenzoic acid;-   3-(4-imidazolyl)acrylic acid;-   2-phenyl-5-benzimidazole sulfonic acid;-   N,N,N-trimethyl-alpha-(2-oxo-3-bornylidene)-p-toluidinium methyl    sulfate;-   5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid, sodium salt;-   3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxy-N,N,N-trimethyl-1-propanaminium    chloride;-   3-[4-(2H-benzotriazol-2-yl)-3-hydroxyphenoxy]-2-hydroxy-N,N,N-trimethyl-1-propanaminium,    chloride;-   2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole; or-   2,2′-dihydroxy-4,4′-dimethoxybenzophenone (Uvinul® 3049).

For instance, suitable UV absorbers are selected from

-   3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonic    acid monosodium salt;-   3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamic acid    and sodium salt;-   2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;-   2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;-   4,6-bis(2,4-dimethylphenyl)-2-(4-(3-dodecyloxy*-2-hydroxypropoxy)-2-hydroxyphenyl)-s-triazine    (*is mixture of C₁₂₋₁₄oxy isomers);-   12-hydroxy-3,6,9-trioxadodecyl    3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamate;-   2,4-dihydroxybenzophenone;-   2,2′-dihydroxy-4,4′-dimethoxy-5,5′-disulfobenzophenone, disodium    salt;-   2,2′,4,4′-tetrahydroxybenzophenone;-   3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxy-N,N,N-trimethyl-1-propanaminium    chloride;-   3-[4-(2H-benzotriazol-2-yl)-3-hydroxyphenoxy]-2-hydroxy-N,N,N-trimethyl-1-propanaminium,    chloride;-   5-benzoyl-4-hydroxy-2-methoxy-benzenesulfonic acid, sodium salt; or-   2-(2-hydroxy-3-alpha-cumyl-5-tert-octylphenyl)-2H-benzotriazole.

Additional suitable antioxidants are for example selected from thehindered phenolic and benzofuranone stabilizers.

Suitable antioxidants are for example selected from the group consistingof

The hindered amine light stabilizers (HALS) of component (c) are forexample known commercial compounds. They are for example selected fromthe group consisting of

-   bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,    bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate,    bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,    n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic    acid-bis(1,2,2,6,6-pentamethylpiperidyl)ester, the condensate of    1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic    acid, the condensate of    N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and    4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,    tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,    tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetraoate,    1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),    4-benzoyl-2,2,6,6-tetramethylpiperidine,    4-stearyloxy-2,2,6,6-tetramethylpiperidine,    bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,    3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,    the condensate of    N,N-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and    4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of    2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine    and 1,2-bis(3-aminopropylamino)ethane, the condensate of    2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine    and 1,2-bis(3-aminopropylamino)ethane,    8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro-[4.5]decane-2,4-dione,    3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,    3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)-pyrrolidine-2,5-dione,    a mixture of 4-hexadecyloxy- and    4-stearyloxy-2,2,6,6-tetramethylpiperidine, the condensate of    N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and    4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensate of    1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine    and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS reg. No.    [136504-96-6]);    (2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,    (1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,    2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-di-aza-4-oxo-spiro[4,5]decane,    the reaction product of    7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane    and epichlorohydrin,    tetra(2,2,6,6-tetramethylpiperidin-4-yl)-butane-1,2,3,4-tetracarboxylate,    tetra(1,2,2,6,6-pentamethylpiperidin-4-yl)-butane-1,2,3,4-tetracarboxylate,    2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]-heneicosan,    8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4,5]-decane-2,4-dione,

wherein m is a value from 5-50,

The complex formers of component (c) are for example nitrogen-containingcomplex formers or polyanionically-derived natural polysaccharides, forexample those containing phosphate, phosphonate or methylphosphonategroups, such as chitin derivatives, e.g. sulfochitin,carboxymethylchitin, phosphochitin or chitosan derivatives, for examplesulfochitosan, carboxymethylchitosan or phosphochitosan.

The complex formers are for example selected from the group consistingof ethylenediaminetetracetic acid (EDTA), nitrilotriacetic acid (NTA),beta-alaninediacetic acid (EDETA) or ethylenediaminedisuccinic acid(EDDS),

aminetrimethylenephosphoric acid (ATMP) conforming to formula

serinediacetic acid (SDA) conforming to formula

asparaginediacetic acid conforming to formula

methylglycinediacetic acid (MGDA) conforming to formula

The present stabilizer systems are particularly suitable for stabilizingbody care products, in particular for use in skin-care products, as bathand shower products, preparations containing fragrances and odoriferoussubstances, hair-care products, dentifrices, deodorizing andantiperspirant preparations, decorative preparations, light protectionformulations and preparations containing active ingredients.

Suitable skin-care products are, in particular, body oils, body lotions,body gels, treatment creams, skin protection ointments, shavingpreparations, such as shaving foams or gels, skin powders, such as babypowder, moisturising gels, moisturising sprays, revitalising bodysprays, cellulite gels and peeling preparations.

Preparations containing fragrances and odoriferous substances are inparticular scents, perfumes, toilet waters and shaving lotions(aftershave preparations).

Suitable hair-care products are, for example, shampoos for humans andanimals, in particular dogs, hair conditioners, products for styling andtreating hair, perming agents, hair sprays and lacquers, hair gels, hairfixatives and hair dyeing or bleaching agents.

Suitable dentifrices are in particular tooth creams, toothpastes,mouth-washes, mouth rinses, anti-plaque preparations and cleaning agentsfor dentures.

Suitable decorative preparations are in particular lipsticks, nailvarnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders,depilatory agents and suntan lotions.

Suitable cosmetic formulations containing active ingredients are inparticular hormone preparations, vitamin preparations, vegetable extractpreparations and antibacterial preparations.

The present body care products can be in the form of creams, ointments,pastes, foams, gels, lotions, powders, make-ups, sprays, sticks oraerosols. The present stabilizer systems may be present in the oil phaseor in the aqueous or aqueous/alcoholic phase.

The additives of component (b) are present, for example, in the bodycare and household products in a concentration of about 5 to about 10000ppm, based on the total formulation by weight, for example from about 10to about 5000 ppm, for example from about 100 to about 5000 ppm. Forexample the additives of component (b) are present in the body care andhousehold products in a concentration of about 5, 10, 15, 20, 25, 35,40, 45 or 50 ppm, based on the total formulation by weight. For example,the additives of component (b) are present from about 5 to about 5000ppm in the formulations (compositions) of this invention.

Laundry detergents, fabric softeners or other products, from which theadditives of component (b) are intended for deposition onto fabrics withuse, are considered household products of this invention, and the aboveconcentration levels also pertain thereto. The present additives ofcomponent (b) are effective at stabilizing the laundry detergents andfabric softeners, as well as the fabrics treated therewith.

Creams are oil-in-water emulsions containing more than 50% water. Theoil-containing base used therein is usually mainly fatty alcohols, forexample lauryl, cetyl or stearyl alcohol, fatty acids, for examplepalmitic or stearic acid, liquid to solid waxes, for exampleisopropylmyristate or beeswax and/or hydrocarbon compounds, such asparaffin oil. Suitable emulsifiers are surfactants having primarilyhydrophilic properties, such as the corresponding non-ionic emulsifiers,for example fatty acid esters of polyalcohols of ethylene oxide adducts,such as polyglycerol fatty acid ester or polyoxyethylenesorbitan fattyacid ether (Tween trademarks); polyoxyethylene fatty alcohol ether ortheir esters or the corresponding ionic emulsifiers, such as the alkalimetal salts of fatty alcohol sulfonates, sodium cetyl sulfate or sodiumstearyl sulfate, which are usually used together with fatty alcohols,such as cetyl alcohol or stearyl alcohol. In addition, creams containagents which reduce water loss during evaporation, for examplepolyalcohols, such as glycerol, sorbitol, propylene glycol, and/orpolyethylene glycols.

Ointments are water-in-oil emulsions which contain up to 70%, forinstance not more than 20 to 50%, of water or of an aqueous phase. Theoil-containing phase contains predominantly hydrocarbons, such asparaffin oil and/or solid paraffin which for instance contains hydroxycompounds, for example fatty alcohol or their esters, such as cetylalcohol or wool wax for improving the water absorption. Emulsifiers arecorresponding lipophilic substances, such as sorbitan fatty acid ester.In addition, the ointments contain moisturisers such as polyalcohols,for example glycerol, propylene glycol, sorbitol and/or polyethyleneglycol as well as preservatives.

Rich creams are anhydrous formulations and are produced on the basis ofhydrocarbon compounds, such as paraffin, natural or partially syntheticfats, for example coconut fatty acid triglycerides or, for instance,hardened oils and glycerol partial fatty acid esters.

Pastes are creams and ointments containing powdered ingredients whichabsorb secretions, for example metal oxides, such as titanium dioxide orzinc oxide, and also tallow and/or aluminium silicates which bind themoisture or the absorbed secretion.

Foams are liquid oil-in-water emulsions in aerosol form. Hydrocarboncompounds are used, inter alia, for the oil-containing phase, forexample paraffin oil, fatty alcohols, such as cetyl alcohol, fatty acidesters, such as isopropylmyristate and/or waxes. Suitable emulsifiersare, inter alia, mixtures of emulsifiers having predominantlyhydrophilic properties, for example polyoxyethylenesorbitan fatty acidester, and also emulsifiers having predominantly lipophilic properties,for example sorbitan fatty acid ester. Commercially available additivesare usually additionally employed, for example preservatives.

Gels are, in particular, aqueous solutions or suspensions of activesubstances in which gel formers are dispersed or swelled, in particularcellulose ethers, such as methyl cellulose, hydroxyethyl cellulose,carboxymethyl cellulose or vegetable hydrocolloids, for example sodiumalginate, tragacanth or gum Arabic and polyacrylate thickener systems.The gels for example additionally contain polyalcohols, such aspropylene glycol or glycerol as moisturisers and wetting agents, such aspolyoxyethylenesobitan fatty acid ester. The gels furthermore containcommercially available preservatives, such as benzyl alcohol, phenethylalcohol, phenoxyethanol and the like.

The following is a list of examples of body care products of thisinvention and their ingredients:

Body care product Ingredients moisturising cream vegetable oil,emulsifier, thickener, perfume, water, antioxidant, UV absorbers shampoosurfactant, emulsifier, preservatives, perfume, antioxidant, UVabsorbers toothpaste cleaning agent, thickener, sweetener, flavor,colorant, antioxidant, water, UV absorbers lip-care stick vegetable oil,wax, TiO₂, antioxidant, UV absorbers

The present body care products, household products, textiles and fabricshave high stability towards color changes and chemical degradation ofthe ingredients present in these products. For example, presentcompositions that comprise a dye are found to have excellent colorstability.

Accordingly, the present invention further pertains to a stabilizedcomposition comprising

-   -   (a) a body care product, household product, textile or fabric,    -   (b) an effective stabilizing amount of one or more compounds of        formula (I), and    -   (d) a dye.

Dyes according to the present invention are for example:

-   -   inorganic pigments, for example iron oxide (Iron Oxide Red, Iron        Oxide Yellow, Iron Oxide Black, etc.), Ultramarines, Chromium        Oxide Green or Carbon Black;    -   natural or synthetic organic pigments;    -   disperse dyes which may be solubilzed in solvents like direct        hair dyes of the HC type, for example HC Red No. 3, HC Blue No.        2 and all other hair dyes listed in International Cosmetic        Ingredient Dictionary and Handbook, 7^(th) edition 19997) or the        dispersion dyes listed in Color Index International or Society        of Dyers and Colourists;    -   color varnishes (insoluble salts of soluble dyes, like many Ca-,        Ba- or Al-salts of anionic dyes);    -   soluble anionic or cationic dyes, like acid dyes (anionic),        basic dyes (cationic), direct dyes, reactive dyes or solvent        dyes.

Generally, for the coloration of household- and body care products allsubstances are suitable which have an absorption in the visible light ofelectromagnetic radiation (wavelength of ca. 4000 to 700 nm). Theabsorption is often caused by the following chromophores:

Azo- (mono-, di, tris-, or poly-)stilbene-, carotenoide-, diarylmethan-,triarylmethan-, xanthen-, acridin-, quinoline, methin- (alsopolymethin-), thiazol-, indamin-, indophenol-, azin-, oxazin, thiazin-,anthraquinone-, indigoid-, phtalocyanine- and further synthetic, naturaland/or inorganic chromophores.

The present stabilizer systems are also used in household cleaning andtreatment agents, for example in laundry products and fabric softeners,liquid cleansing and scouring agents, glass detergents, neutral cleaners(all-purpose cleaners), acid household cleaners (bath), bathroomcleaners, for instance in washing, rinsing and dishwashing agents,kitchen and oven cleaners, clear rinsing agents, dishwasher detergents,shoe polishes, polishing waxes, floor detergents and polishes, metal,glass and ceramic cleaners, textile-care products, rug cleaners andcarpet shampoos, agents for removing rust, color and stains (stainremover salt), furniture and multipurpose polishes and leather and vinyldressing agents (leather and vinyl sprays) and solid and liquid airfresheners.

The present invention also concerns home care and fabric care productssuch as drain cleaners, disinfectant solutions, upholstery cleaners,automotive care products (e.g., to clean and/or polish and protectpaint, tires, chrome, vinyl, leather, fabric, rubber, plastic andfabric), degreasers, polishes (glass, wood, leather, plastic, marble,granite, and tile, etc.), and metal polishes and cleaners. Antioxidantsare suitable to protect fragrances in above products as well as in dryersheets. The present invention also relates to home care products such ascandles, gel candles, air fresheners and fragrance oils (for the home).

The stabilizers of the present invention may be employed in fabrictreatment that takes place after use of the fabric, referred to asfabric care. Such treatments include laundering, which uses detergentsand/or fabric conditioner, and the application of non-detergent basedfabric care products, such as spray-on products. When employed in thisfashion, the present stabilizers are intended for deposition onto thefabric and used to protect the fabric, colorants and fragrancesassociated with said these fabrics from environmental damage.

Typical examples of household cleaning and treating agents are:

Household cleaners/household treating agents Ingredients detergentsurfactant mixture, ethanol, antioxidant, water, concentrate UVabsorbers, antioxidant shoe polish wax, wax emulsifier, antioxidant,water, preservative, UV absorbers, antioxidant wax-containing flooremulsifier, wax, sodium chloride, antioxidant, cleaning agent water,preservative, UV absorbers, antioxidant

The present stabilizers are for example incorporated by dissolution inan oil phase or alcoholic or water phase, where required at elevatedtemperature.

The present invention also pertains to a method of stabilizing a bodycare product, household product, textile or fabric, which comprisesincorporating therein or applying thereto one or more compounds of theformulae (III) to (IIIc), for example one or more compounds of theformulae A* to EE*.

In the case of stabilized fabrics, for example dyed fabrics, the presentstabilizers are applied thereto via deposition from for instancedetergents, fabric conditioners or non-detergent based fabric careproducts.

The present fabrics are natural or synthetic, and may be woven ornonwoven.

The present invention also pertains to a method of stabilizing a bodycare product, household product, textile or fabric, each of whichcontain a dye, which comprises incorporating therein or applying theretoone or more compounds of the formulae (III) to (IIIc), for example oneor more compounds of the formulae A* to EE*. The stabilizers of formulae(III) to (IIIc) are very effective towards the stabilization of dyes inthe present compositions.

The textiles of this invention are for example textile fiber materials,for example nitrogen-containing or hydroxy-group-containing fibermaterials, for instance textile fiber materials selected from cellulose,silk, wool, synthetic polyamides, leather and polyurethanes. Includedare cotten, linen and hemp, pulp and regenerated cellulose. Includedalso are cellulosic blends, for example mixtures of cotton and polyamideor cotton/polyester blends.

The additives of the present invention are for example applied totextiles in a dyeing or printing process, or in a finishing process. Forinstance, the additives may be applied as part of a dye formulation. Theadditives may be applied to textiles for example in an ink-jet printingprocess. The additives are for example applied as part of an aqueous dyesolution or printing paste. They may be applied in an exhaust method ordyeing by the padder dyeing method, in which the textiles areimpregnated with aqueous dye solutions, which may contain salts, and thedyes and additives are fixed, after an alkali treatment or in thepresence of alkali, if appropriate with the action of heat or by storageat room temperature for several hours. After fixing, the dyeings orprints are rinsed thoroughly with cold and hot water, if appropriatewith the addition of an agent which has a dispersing action and promotesdiffusion of the non-fixed portions.

The dye or ink formulations for application to textiles may comprisefurther customary additives, for example surfactants, antifoams,antimicrobials and the like, for example as disclosed in U.S. Pat. Nos.6,281,339, 6,353,094 and 6,323,327, the disclosures of which are herebyincorporated by reference.

The following Examples illustrate the invention. Percentages are inweight percent unless indicated otherwise.

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle.

The bottles are also exposed to accelerated fluorescent lighting,Philips, 40 Watt, Daylight Deluxe (D65), full exposure to light.

EXAMPLE 1

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine (5g, 0.02 mole), citric acid (1.43 g, 0.0067 mole) and methanol (50 g, 1.6mole) are added to a round bottom flask. The mixture is stirred atambient temperature for 30 minutes to ensure complete dissolution. Themethanol is removed by distillation and the resulting solid product isdried to constant weight. The title compound is obtained (6 g, 93%yield) as a white solid with a melting point of 112-122 C whosestructure is consistent with HNMR. The HNMR spectrum indicates a ratioof about four to one.

¹H NMR (CD₃OD): δ 3.88 (t, 1H), 3.63 (s, 2H), 2.84 (s, 4H), 1.74 (d,2H), 1.42 (t, 2H), 1.23 (s, 6H), 1.21 (s, 6H), 1.20 (s, 6H).

EXAMPLE 2

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine (5g, 0.02 mole), citric acid (2.13 g, 0.01 mole) and methanol (50 g, 1.6mole) are added to a round bottom flask. The mixture is stirred atambient temperature for 30 minutes to ensure complete dissolution. Themethanol is removed by distillation and the resulting solid product isdried to constant weight. The title compound is obtained (6.4 g, 90%yield) as a white solid with a melting point of 103-113 C whosestructure is consistent with HNMR. The HNMR spectrum indicates a ratioof about 2.5 to one.

¹H NMR (CD₃OD): δ 3.88 (t, 1H), 3.63 (s, 2H), 2.84 (s, 4H), 1.74 (d,2H), 1.42 (t, 2H), 1.23 (s, 6H), 1.21 (s, 6H), 1.20 (s, 6H).

EXAMPLE 3

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine (5g, 0.02 mole), citric acid (4.29 g, 0.02 mole) and methanol (50 g, 1.6mole) are added to a round bottom flask. The mixture is stirred atambient temperature for 30 minutes to ensure complete dissolution. Themethanol is removed by distillation and the resulting solid product isdried to constant weight. The title compound is obtained (8.6 g, 92.5%yield) as a white solid with a melting point of 93-110 C whose structureis consistent with HNMR. The HNMR spectrum indicates a ratio of aboutone to one.

¹H NMR (CD₃OD): δ 3.88 (t, 1H), 3.63 (s, 2H), 2.84 (s, 4H), 1.75 (d,2H), 1.42 (t, 2H), 1.23 (s, 6H), 1.21 (s, 6H), 1.20 (s, 6H).

EXAMPLE 4

4-Hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine (5g, 0.02 mole), ascorbic acid (3.59 g, 0.02 mole) and methanol (200 g,6.2 mole) are added to a round bottom flask. The mixture is stirred atambient temperature for 60 minutes to ensure complete dissolution. Themethanol is removed by distillation and the resulting solid product isdried to constant weight. The title compound is obtained (8.1 g, 94%yield) as a white solid with a melting point of 131-137 C whosestructure is consistent with HNMR. The HNMR spectrum indicates a ratioof about one to one.

¹H NMR (CD₃OD): δ 4.79 (s, 1H), 3.89 (t, 2H), 3.88 (t, 1H), 3.67 (d,1H), 3.63 (s, 2H), 1.74 (d, 2H), 1.42 (t, 2H), 1.22 (s, 6H), 1.20 (s,6H), 1.20 (s, 6H).

EXAMPLE 5

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compounds(0.36 g) are dissolved in 5 mL of methanol which is then added to 120 gof shampoo (Suave® R Natural Fresh Mountain Strawberry Shampoo) withagitation. The stabilized shampoo formulation is agitated for 15 minutesand put into 20 mL glass scintillation vials. These formulations areweathered under fluorescent light aging at ambient temperature. TheCIEL*a*b coordinates before and after exposure are measured using X-Rite938 Spectrodensitometer. Color change is expressed as Delta E (DE). Thecolor change is given by Delta E (DE) which is calculated by:DE=[(DL*)²+(Da*)²+(Db*)²]^(1/2)

Stabilizer DE after (loading at 0.30 wt %) 4 weeks None 21.6 Compound A15.6 Example 3 12.3 Example 2 12.1 Example 1 11.7

Compound A is 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine which isdisclosed in WO 2003103622, the publication of U.S. Pat. app. No.60/377,381, filed May 2, 2002, incorporated herein by reference.

The compounds according to this invention are able to improve clearlythe light fastness of shampoo formulations.

EXAMPLE 6

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compounds(0.36 g) are dissolved in 5 mL of methanol which is then added to 120 gof shampoo (Clairol® Herbal Essences Shampoo) with agitation. Thestabilized shampoo formulation is agitated for 15 minutes and put into20 mL glass scintillation vials. These formulations are weathered underfluorescent light aging at ambient temperature. The CIEL*a*b coordinatesbefore and after exposure are measured using X-Rite 938Spectrodensitometer. Color change is expressed as Delta E (DE).

Stabilizer DE after (loading at 0.30 wt %) 1 week Compound A 1.32Example 2 0.95 Example 1 0.87

Compound A is 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine which isdisclosed in WO2003103622, the publication of U.S. Pat. app. No.60/377,381, filed May 2, 2002, incorporated herein by reference.

The compounds according to this invention are able to improve clearlythe light fastness of shampoo formulations.

EXAMPLE 7

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds (0.36 g) are dissolved in 5 mL of methanol which is then addedto 120 g of mouthwash (Scope® Original Mint) with agitation. Thestabilized mouthwash formulation is agitated for 15 minutes and put into20 mL glass scintillation vials. These formulations are weathered underfluorescent light aging at ambient temperature. The CIEL*a*b coordinatesbefore and after exposure are measured using X-Rite 938Spectrodensitometer. Color change is expressed as Delta E (DE).

Stabilizer DE after (loading at 0.30 wt %) 1 week None 3.26 Compound A2.93 Example 1 2.45 Example 2 1.98

Compound A is 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine which isdisclosed in WO 2003103622, the publication of U.S. Pat. app. No.60/377,381, filed May 2, 2002, incorporated herein by reference.

The compounds according to this invention are able to improve clearlythe light fastness of mouthwash formulations.

EXAMPLE 8

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds (0.36 g) are dissolved in 5 mL of methanol which is then addedto 120 g of mouthwash (Listerine® Tartar Control Wintermint) withagitation. The stabilized mouthwash formulation is agitated for 15minutes and put into 20 mL glass scintillation vials. These formulationsare weathered under fluorescent light aging at ambient temperature. TheCIEL*a*b coordinates before and after exposure are measured using X-Rite938 Spectrodensitometer. Color change is expressed as Delta E (DE).

Stabilizer DE after (loading at 0.30 wt %) 1 week Compound A 9.23 None1.17 Example 1 0.69 Example 3 0.66 Example 2 0.60

Compound A is 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine which isdisclosed in WO 2003103622, the publication of U.S. Pat. app. No.60/377,381, filed May 2, 2002, incorporated herein by reference.

The compounds according to this invention are able to improve clearlythe light fastness of mouthwash formulations.

EXAMPLE 9

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compoundsare dissolved in a shampoo formulation with agitation.3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonicacid monosodium salt, a benzotriazole UV absorber, is added to theshampoo formulation. These formulations are weathered under fluorescentlight at ambient temperature. The CIEL*a*b coordinates before and afterexposure are measured. The change in color is expressed by Delta E (DE).The compounds according to this invention are quite efficacious inimproving light fastness of shampoo formulations.

EXAMPLE 10

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compoundsare dissolved in a shampoo formulation with agitation. An s-triazine UVabsorber is added to the shampoo formulation. These formulations areweathered under fluorescent light at ambient temperature. The CIEL*a*bcoordinates before and after exposure are measured. The change in coloris expressed by Delta E (DE). The compounds according to this inventionare quite efficacious in improving light fastness of shampooformulations.

EXAMPLE 11

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compoundsare dissolved in a shampoo formulation with agitation. A benzophenone UVabsorber is added to the shampoo formulation. These formulations areweathered under fluorescent light at ambient temperature. The CIEL*a*bcoordinates before and after exposure are measured. The change in coloris expressed by Delta E (DE). The compounds according to this inventionare quite efficacious in improving light fastness of shampooformulations.

EXAMPLE 12

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds are added to a mouthwash formulation with agitation.3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonicacid monosodium salt, a benzotriazole UV absorber, is added to themouthwash formulation. These formulations are weathered underfluorescent lighting at ambient temperature. The CIEL*a*b coordinatesbefore and after exposure are measured. Color change is expressed asDelta E (DE). The compounds according to this invention are quiteefficacious in improving light fastness of mouthwash formulations.

EXAMPLE 13

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds are added to a mouthwash formulation with agitation. Ans-triazine UV absorber is added to the mouthwash formulation. Theseformulations are weathered under fluorescent lighting at ambienttemperature. The CIEL*a*b coordinates before and after exposure aremeasured. Color change is expressed as Delta E (DE). The compoundsaccording to this invention are quite efficacious in improving lightfastness of mouthwash formulations.

EXAMPLE 14

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds are added to a mouthwash formulation with agitation. Abenzophenone UV absorber is added to the mouthwash formulation. Theseformulations are weathered under fluorescent lighting at ambienttemperature. The CIEL*a*b coordinates before and after exposure aremeasured. Color change is expressed as Delta E (DE). The compoundsaccording to this invention are quite efficacious in improving lightfastness of mouthwash formulations.

EXAMPLE 15

An aqueous based test formulation is prepared as follows:

sodium laureth sulfate (30%, TEXAPON NSO, Cognis) 30%cocamidopropylbetaine (30%, DEHYTON K, Cognis) 10% colorant* 0.001%  instant stabilizer 0.05%   citric acid (10% aqueous solution) to pH 6deionized water to 100% *Colorant is PURICOLOR BLUE ABL9 (FD&C Blue No.1)

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are exposed in an AtlasCi-65 Xenon arc WeatherOmeter, AATCC Test Method 16. Color measurementsare performed on a Hunter Ultrascan XE spectrophotometer. Delta L, a andb values are the difference between the initial values and the values ateach interval. It is seen that the stabilizers of the present inventionprovide excellent color stability in personal care products.

EXAMPLE 16

An aqueous based test formulation is prepared as follows:

sodium laureth sulfate (30%, TEXAPON NSO, Cognis) 30%cocamidopropylbetaine (30%, DEHYTON K, Cognis) 10% colorant* 0.001%instant stabilizer 0.05% citric acid (10% aqueous solution) to pH 6deionized water to 100% *Colorant is PURICOLOR RED ARE33 (FD&C Red No.33).

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are exposed in an AtlasCi-65 Xenon arc WeatherOmeter, AATCC Test Method 16, option E. Colormeasurements are performed on a Hunter Ultrascan XE spectrophotometer.Delta L, a and b values are the difference between the initial valuesand the values at each interval. It is seen that the stabilizers of thepresent invention provide excellent color stability in personal careproducts.

EXAMPLE 17

An aqueous based test formulation is prepared as follows:

sodium laureth sulfate (30%, TEXAPON NSO, Cognis) 30%cocamidopropylbetaine (30%, DEHYTON K, Cognis) 10% colorant* 0.001%instant stabilizer 0.05% citric acid (10% aqueous solution) to pH 6deionized water to 100% *Colorant is FD&C Red No. 40.

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are exposed in an AtlasCi-65 Xenon arc WeatherOmeter, AATCC Test Method 16. Color measurementsare performed on a Hunter Ultrascan XE spectrophotometer. Delta L, a andb values are the difference between the initial values and the values ateach interval. It is seen that the stabilizers of the present inventionprovide excellent color stability in personal care products.

EXAMPLE 18

An aqueous based test formulation is prepared as follows:

sodium laureth sulfate (30%, TEXAPON NSO, Cognis) 30%cocamidopropylbetaine (30%, DEHYTON K, Cognis) 10% colorant* 0.001%  instant stabilizer 0.05%   citric acid (10% aqueous solution) to pH 6deionized water to 100% *Colorant is PURICOLOR BLUE ABL9 (FD&C Blue No.1)

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are also exposed toaccelerated fluorescent lighting, Philips, 40 Watt, Daylight Deluxe(D65), full exposure to light. Color measurements are performed on aHunter Ultrascan XE spectrophotometer. Delta L, a and b values are thedifference between the initial values and the values at each interval.It is seen that the stabilizers of the present invention provideexcellent color stability in personal care products.

EXAMPLE 19

An aqueous based test formulation is prepared as follows:

sodium laureth sulfate (30%, TEXAPON NSO, Cognis) 30%cocamidopropylbetaine (30%, DEHYTON K, Cognis) 10% colorant* 0.001%  instant stabilizer 0.05%   citric acid (10% aqueous solution) to pH 6deionized water to 100% *Colorant is PURICOLOR RED ARE33 (FD&C Red No.33).

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are also exposed toaccelerated fluorescent lighting, Philips, 40 Watt, Daylight Deluxe(D65), full exposure to light. Color measurements are performed on aHunter Ultrascan XE spectrophotometer. Delta L, a and b values are thedifference between the initial values and the values at each interval.It is seen that the stabilizers of the present invention provideexcellent color stability in personal care products.

EXAMPLE 20

An aqueous based test formulation is prepared as follows:

sodium laureth sulfate (30%, TEXAPON NSO, Cognis) 30%cocamidopropylbetaine (30%, DEHYTON K, Cognis) 10% colorant* 0.001%  instant stabilizer 0.05%   citric acid (10% aqueous solution) to pH 6deionized water to 100% *Colorant is FD&C Red No. 40.

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are also exposed toaccelerated fluorescent lighting, Philips, 40 Watt, Daylight Deluxe(D65), full exposure to light. Color measurements are performed on aHunter Ultrascan XE spectrophotometer. Delta L, a and b values are thedifference between the initial values and the values at each interval.It is seen that the stabilizers of the present invention provideexcellent color stability in personal care products.

EXAMPLE 21

The components of phase A are thoroughly mixed in a homogenizer for 10min at 75-80° C. The water phase B, likewise heated to 75-80° C.beforehand, is slowly added and the mixture is homogenized for 1 min.The mixture is cooled, with stirring, to 40° C. and then phases C and Eare added and the mixture is homogenized for 1 min. Subsequently, phaseD is added and the mixture is homogenized for ½ min and cooled, withstirring, to room temperature.

Phase Ingredients (w/w) % A passionflower oil 8 glyceryl dioleate 4dicapryl ether 4 Isopropylisostearate 4 instant stabilizer 0.05 B water,demin. ad. 100 EDTA 0.1 C Carbomer 0.15 D sodium hydroxide 10% 0.20 Eperfume; preservative q.s.

It is seen that the stabilizers of the present invention provideexcellent color stability in personal care products.

EXAMPLE 22

The components below are thoroughly mixed in the cited sequence at 50°C., a clear homogeneous solution being obtained. The UV absorber is, forexample,3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonicacid monosodium salt.

Ingredients (w/w) % ethanol, 96% 60 d-limonene 5 cedrene 1.5 citronellol0.5 savin 0.5 instant stabilizer 0.08 UV absorber 0.1 S,S-EDDS 0.005colorant (D&C Yellow No. 5) 0.02 water ad. 100

Excellent results are achieved for this example of a toilet waterformulation.

EXAMPLE 23

The hydroxypropyl cellulose is first predissolved in half of the alcohol(Vortex mixer) and is charged with the aminomethylpropanol. The othercomponents—with the exception of the acrylate resin—are dissolved inalcohol and this solution is added, with stirring, to the hydroxypropylcellulose. Subsequently, the acrylate resin is added and stirred untilcompletely dissolved. The UV absorber used is, for example,benzophenone-4 is 5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid,sodium salt.

Ingredients (w/w) % alcohol, anhydrous 96.21 octylacrylamide/ 2.52acrylate/butylaminoethylmethacrylate copolymer hydroxypropyl cellulose0.51 aminomethylpropanol (95%) 0.46 instant stabilizer 0.05 UV absorber0.05 perfume oil 0.20

Excellent results are achieved for this example of a hair styling sprayformulation.

EXAMPLE 24

The components listed below are mixed, with stirring, at roomtemperature until they are completely dissolved. The pH is 6.5. The UVabsorber is, for example,2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole.

Ingredients (w/w) % sodium myreth sulfate 50.00 TEA abietoyl collagenhydrolysate 3.50 laureth-3 3.00 colorant (D&C Red No. 33) 0.20 instantstabilizer 0.05 UV absorber 0.15 phosphonomethylchitosan, sodium salt0.01 perfume oil 0.10 water ad. 100

Excellent results are achieved for this example of a shampoo compositionfor oily hair.

EXAMPLE 25

The stabilizer is predissolved in the terpene. The components are thenstirred in the cited sequence at about 65° C. until homogeneous. Themixture is then cooled to room temperature.

Ingredients (w/w) % synthetic soap (Zetesap 813) 7.85 Glycerol 6.00anionic surfactant (Lumorol 4192; 22.00 Mulsifan RT 13) Vaseline 11.00paraffin 52/54 20.00 Talcum 2.00 orange terpene 4.00 instant stabilizer0.02 Water 27.13

Excellent results are achieved for this example of a leather dressingand cleaning agent composition.

EXAMPLE 26

The components listed below are dissolved in the cited sequence until aclear homogeneous mixture is obtained.

Ingredients (w/w) % anionic/amphoteric 0.7 surfactants (Lumorol RK)butyl glycol 5.0 Isopropanol 20.0 d-limonene 4.00 instant stabilizer0.02 water, demin. ad. 100

Excellent results are achieved for this example of a glass detergentformulation.

EXAMPLE 27

The instant stabilizers are each deposited (from water) on a dyed cottonfabric at 0.05, 0.1, 0.2, 0.5 and 1.0 percent by weight, based on theweight of the cotton. The dyed fabrics contain the following dyes at0.05, 0.1, 0.2 and 0.5 percent by weight based on cotton. This resultsin 60 separate formulations for each dye listed:

Scarlet HE-3G

Crimson HE-XL

Yellow HE-6G

Red HE-XL

Blue HE-XL

Turquoise H-A

Navy HE-XL

Remazol

Red RB

Brilliant Red RBS

Orange FR

Navy CG

Turquoise G

Black B

The cotton fabrics are subjected to light exposure in an Atlas Ci-65Xenon arc WetherOmeter or to accelerated fluorescent lighting. Thepresent stabilizers provide outstanding color protection to the dyedfabrics. This experiment simulates dye protection achievable throughdeposition of the present stabilizers via treatment with, for example,stabilizer-containing laundry detergent or fabric conditioner.

EXAMPLE 28

The instant stabilizers and UV absorbers, for example3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonicacid monosodium salt, are each deposited (from water) on a dyed cottonfabric at 0.05, 0.1, 0.2, 0.5 and 1.0 percent by weight, based on theweight of the cotton. The dyed fabrics contain the following dyes at0.05, 0.1, 0.2 and 0.5 percent by weight based on cotton. This resultsin 60 separate formulations for each dye listed:

Scarlet HE-3G

Crimson HE-XL

Yellow HE-6G

Red HE-XL

Blue HE-XL

Turquoise H-A

Navy HE-XL

Remazol

Red RB

Brilliant Red RBS

Orange FR

Navy CG

Turquoise G

Black B

The cotton fabrics are subjected to light exposure in an Atlas Ci-65Xenon arc WetherOmeter or to accelerated fluorescent lighting. Thepresent stabilizers provide outstanding color protection to the dyedfabrics. This experiment simulates dye protection achievable throughdeposition of the present stabilizers via treatment with for examplestabilizer-containing laundry detergent or fabric conditioner.

1. A stabilized composition comprising (a) a body care product selectedfrom the group consisting of skin-care products, hair-care products,dentifrices, and deodorizing and antiperspirant preparations, and (b)from about 5 ppm to about 10000 ppm, based on the total formulation byweight, of one or more compounds selected from the group consisting offormulae (B*)

wherein E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12carbon atoms or aralkoxy of 7 to 15 carbon atoms, or E is —O-T-(OH)_(b),T is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbonatoms, a straight or branched chain alkylene of 1 to 4 carbon atomssubstituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms; b is 1, 2 or 3 with the proviso that bcannot exceed the number of carbon atoms in T, and when b is 2 or 3,each hydroxyl group is attached to a different carbon atoms of T; R ishydrogen or methyl; and in formula (B*), m is 1 to 4, and when m is 1,R₂ is cycloalkyl of 5 to 12 carbon atoms, when m is 2, cycloalkylene of5 to 12 carbon atoms, aralkylene of 7 to 15 carbon atoms or arylene of 6to 12 carbon atoms, when m is 3, R₂ is alkanetriyl of 3 to 8 carbonatoms or benzenetriyl, or when m is 4, R₂ is alkanetetrayl of 5 to 8carbon atoms or benzenetetrayl, HY is an inorganic or organic acid;wherein the total charge of cations is equal to the total charge ofanions; and Y is selected from the group consisting of phosphate,phosphonate, carbonate, bicarbonate, nitrate, chloride, bromide,bisulfite, sulfite, bisulfate, sulfate, borate, formate, acetate,benzoate, citrate, oxalate, tartrate, acrylate, polyacrylate, fumarate,maleate, itaconate, glycolate, gluconate, malate, mandelate, tiglate,ascorbate, polymethacrylate, a carboxylate of nitrilotriacetic acid, acarboxlylate of hydroxyethylethylenediaminetriacetic acid, a carboxylateof ethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, a carboxylate ofdiethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, alkylsulfonate, arylsulfonate, andalkyl-substituted arylsulfonate.
 2. A stabilized composition accordingto claim 1, wherein E is alkoxy of 1 to 10 carbon atoms, cycloalkoxy of5 to 8 carbon atoms or aralkoxy of 7 to 12 carbon atoms, or E is—O-T-(OH)_(b), T is a straight or branched chain alkylene of 1 to 10carbon atoms, cycloalkylene of 5 to 10 carbon atoms, cycloalkenylene of5 to 10 carbon atoms, a straight or branched chain alkylene of 1 to 4carbon atoms substituted by phenyl or by phenyl substituted by one ortwo alkyl groups of 1 to 4 carbon atoms; b is 1, 2 or 3 with the provisothat b cannot exceed the number of carbon atoms in T, and when b is 2 or3, each hydroxyl group is attached to a different carbon atoms of T; Ris hydrogen; when m is 2, R₂ is alkylene of 1 to 8 carbon atoms oralkenylene of 4 to 8 carbon atoms, HY is an inorganic or organic acid;wherein the total charge of cations is equal to the total charge ofanions; and Y is phosphate, phosphonate, carbonate, bicarbonate,chloride, bromide, bisulfate, sulfate, borate, formate, acetate,benzoate, citrate, oxalate, tartrate, acrylate, fumarate, maleate,itaconate, glycolate, gluconate, malate, mandelate, tiglate, ascorbate,a carboxylate of nitrilotriacetic acid, a carboxylate ofhydroxyethylethylenediaminetriacetic acid, a carboxylate ofethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, a carboxylate ofdiethylenediaminetetracetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, alkylsulfonate, arylsulfonate, oralkyl-substituted arylsulfonate.
 3. A stabilized composition accordingto claim 2, wherein E is alkoxy of 1 to 10 carbon atoms, cycloalkoxy of5 to 8 carbon atoms or aralkoxy of 7 to 12 carbon atoms, or E is—O-T-(OH)_(b), T is a straight or branched chain alkylene of 1 to 10carbon atoms, cycloalkylene of 5 to 10 carbon atoms, cycloalkenylene of5 to 10 carbon atoms, a straight or branched chain alkylene of 1 to 4carbon atoms substituted by phenyl or by phenyl substituted by one ortwo alkyl groups of 1 to 4 carbon atoms; b is 1, 2 or 3 with the provisothat b cannot exceed the number of carbon atoms in T, and when b is 2 or3, each hydroxyl group is attached to a different carbon atoms of T; Ris hydrogen, when m is 2, R₂ is alkylene of 1 to 8 carbon atoms, HY isan inorganic or organic acid; wherein the total charge of cations isequal to the total charge of anions; and Y is phosphate, phosphonate,carbonate, bicarbonate, chloride, bromide, bisulfate, sulfate, borate,formate, acetate, benzoate, citrate, oxalate, tartrate, ascorbate,acrylate, fumarate, maleate, itaconate, glycolate, gluconate, malate,mandelate, tiglate, a carboxylate of nitrilotriacetic acid, acarboxylate of hydroxyethylethylenediaminetriacetic acid, a carboxylateof ethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, a carboxylate ofdiethylenediaminetetraacetic acid, a carboxylate ofdiethylenetriaminepentaacetic acid, alkylsulfonate, arylsulfonate, oralkyl-substituted arylsulfonate.
 4. A composition according to claim 1further comprising (c) one or more compounds selected from the groupconsisting of the ultraviolet light absorbers, antioxidants, tocopherol,tocopherol acetate, hindered amine light stabilizers, complex formers,optical brighteners, surfactants, and polyorganosiloxanes.
 5. Acomposition according to claim 4 where the ultraviolet light absorbersare selected from the group consisting of 2H-benzotriazoles,s-triazines, benzophenones, alpha-cyanoacrylates, oxanilides,benzoxazinones, benzoates, and alpha-alkyl cinnamates.
 6. A compositionaccording to claim 1 further comprising (d) a dye.
 7. A compositionaccording to claim 1 where the compounds of component (b) are present ina concentration of about 10 to about 5000 ppm based on the totalformulation by weight.
 8. A composition according to claim 1 wherein theskin-care products are selected from the group consisting of body oils,body lotions, body gels, treatment creams, skin protection ointments,shaving preparations, and skin powders.
 9. A composition according toclaim 1 wherein the hair-care products are selected from the groupconsisting of shampoos, hair conditioners, 2 in 1 conditioners, leave inand rinse off conditioners, agents for styling and treating hair,perming agents, relaxants, hair sprays and lacquers, hair dyeingsystems, permanent, demi-permanent, semi-permanent and temporary hairdyeing systems, and hair bleaching agents.